SA515361009B1 - Energy curable sealants - Google Patents

Abstract

Curable compositions containing thiol-terminated polythioethers and encapsulated polyepoxy curing agents are disclosed. The compositions exhibit extended pot life.

Description

— \ — ALB Energy Curable Sealants Full Description

Invention background

The present disclosure relates to hardenable compositions containing de-thioether

thiol-terminated polythioether and polyepoxy coated hardening agent

23a. polyepoxy formulations are useful in aerospace sealing applications as they exhibit 0 jee.

mechanical stress

Sealants are useful in aerospace and other applications that must be

It meets mechanical, chemical and environmental requirements. Fluids can be applied

Leakage on a variety of surfaces including metal surfaces.

10161018013816 coatings and intermediate coatings primer coatings and primers 0; and permeable coatings 5 8060. In fluids finished coatings and final coatings leakage described for example in the US patent No. US Patent No. Terminated with thiol and hardening agents of poly (J) polythio compounds are reacted +”, 4 . Epoxy to provide rigid sealants in the field of aviation and space

1 during applied practice; Sealing compositions may be provided in two-part formulations whereby the thiol-terminated polythioethers and polyepoxy are supplied as separate components; Where the main catalyst is in the polythioether component. as an alternative; The base catalyst can be provided as a third component; The component containing the thiol-terminated polythioether is mixed; the component containing polyepoxy; and the containing component

Yo catalyzed before use BRAT however ¢ Once components are mixed ¢ Reaction continues + life is shortened

ONLY

_ so

Operational in less than VY hours depending on the temperature and type of the main catalyst at least partially. There is a demand for ways to extend the service life of thiol-terminated polythioether formulations using epoxy curing chemistries are desired.

© General description of the invention in feature one; Compositions including ( ) thiol-terminated polythioethers are provided; (b) Epoxy coated polyurethane; and (c) an .amine catalyst in dew sec; Lal formulations are supplied as a sealant comprising (a) thiol-terminated polythioethers; (b) Epoxy coated polyurethane; and (c) an amine catalyst.

in a third dew; Methods provided for sealing an opening include (a) applying a sealing composition comprising thiol-terminated polythioethers and epoxy coated to one or more surfaces defining an opening; and (b) exerting an effort to release the polyepoxy from the encapsulating material. In a fourth aspect, openings are provided which are sealed using a sealant composition according to the current density.

15 Certain embodiments of combinations and methods are now indicated. The embodiments shown here are not intended to limit claims. And on the contrary; The claims shall cover all alternatives, modifications and equivalents. Detailed description:

0 a For the purposes of the following description; It is understood that the embodiments presented in accordance with the present invention may include various alternative step sequences and variations except as expressly indicated to the contrary. Furthermore it; other than as set forth in the ABR or where Gat states otherwise; Each should be understood

ONLY

Numbers expressing for example (JB) the quantities of components used in the description and claims as modified in all cases by the term "about". Accordingly, unless al other than ells, all numerical variables mentioned in the following description and claims The relevant protections are approximations that can vary according to the desired properties to be obtained.At the very least © and not as an attempt to restrict the application of Tae equivalents to the range of claims each numeric variable should be interpreted at least in terms of the number of significant digits mentioned and by Applying ordinary rounding techniques.Although the numeric range values and variables mentioning the wide range of the invention are approximations, the numeric values given in the given examples are reported as accurately as possible.However, any numerical value containing 0 inherently contains certain errors that necessarily result from Normal variation found in the corresponding test measurements. In addition, it should be understood that any digital range mentioned herein is intended to include all sub-range values included in it. For example, it is intended to include a range from 1" to 0 on all sub-values in between (and including) the stated minimum value of about 1 and the stated maximum value of Vo of about 10; i.e. the range includes a minimum value greater than or equal to 1 and a maximum value less than or equal to 01 plus .01 that; in this application; The use of 'or' means 'and/or' unless path is specified otherwise; even if 'and/or' can be explicitly used in certain cases. The dash symbol (-7") is used between two letters or symbols to indicate a bonding point of a substituent group or between two atoms. For example —CONH2 is bonded to a chemical moiety through the carbon atom 0 Alkanediyl " means a binary moiety of a unsaturated group unsaturated fe ie or straight ALL containing for example JE from 1 to YA carbon atoms (01-18); from 1 to 04 carbon atoms (01-14); from 1 to 1 carbon atoms (01-6); from 1 to; carbon atoms ((Cl-d) or from 1 To?hydrocarbon atoms tr

Coe

(01-3). It will be realized that a branched diyl alkane includes a minimum of ? carbon atoms. in embodiments

certain; The diyl alkane is: alkanediyl, 2-10 alkanediyl, 62-8 alkanediyl, 22-6 alkanediyl, 2-14 alkanediyl 62-4; And in embodiments of ‎alkanediyl 62-3 die . Examples of © alkane groups include diylmethane -diyl (-0112-) methane—diyl (-CH2-) ethane = 7-diyl cethane-1,2—diyl (-CH2CH2-) (-CH2CH2-) Propane =? (6013(06112-)) 1-butane-1,4-diyl (CH2CH2CH2CH2-) pentane-1,5-diyl J lo ( -glss (CH2CH2CH2CH2CH2—0>di hexane-1,6-diyl Ji ((CH2CH2CH2CH2CH2CH2) heptane-1-l-1-diyl pentane-1,5-diyl octane-1; lA yl octane—1 066806-1,10-0 dodecane-0” 11 -diyl dodecane—-1,12-diyl "

and the like. Vo the term 'alkanecycloalkane' refers to a saturated hydrocarbon group having one or more cycloalkyl and/or cycloalkanediyl groups and one or more alkyl groups and/or calkanediyl diyl alkane, where cycloalkyl; cycloalkane “alkyl” and diyl alkane are as defined herein. In certain embodiments; each cycloalkyl group(s) and/or 0-microalkan glo yl is “C3-6 05-6; in certain embodiments; cyclohexyl cyclohexyl diyl 07/01006” 80©0. in certain embodiments; each alkyl and/or alkane group(s) Diyl is 61-6; In embodiments of Aime the alkane group cycloalkane “_”alkanecycloalkane 064-18 alkanecycloalkane C4-16 .alkanecycloalkane Yo “ 4-12 ONE Y

-?- “alkanecycloalkane 6-12 .alkanecycloalkane 64-6 calkanecycloalkane calkanecycloalkane C6-10 and in certain embodiments; .alkanecycloalkane C6-9 Examples of cycloalkane groups Je BEST FO oll include tetramethylcyclohexane and cyclohexylmethane . © The term “alkanecycloalkanediyl” refers to the udiradical moiety of the alkanecycloalkane group .alkanecycloalkane in certain embodiments; OB the alkanecycloalkanediyl cycloalkan group is 064-18 alkanecycloalkanediyl 4-16 “alkanecycloalkanediyl” 4-12 C6-12 “alkanecycloalkanediyl C4-8” alkanecycloalkanediyl alkanecycloalkanediyl C6-10 “alkanecycloalkanediyl C6-10 0 ; and in certain embodiments; 66-9 the 2A01081/»80©0/A818060. Examples of diyl cycloalkane groups include BET oF 0 methylcyclohexane-0; go yl 1,1,3,3-tetramethylcyclohexane—1,5—diyl and cyclohexylmethane hE c= yl cyclohexylmethane—4,4'—diyl . VO Alkenyl Jul group “ ” denotes the L(R)2C=C(R)2 group in certain embodiments; An alkyl group has the structural formula —RC=C(R)2 where the alkyl group is a terminal group and is attached to a larger molecule. In Jie these embodiments; Each ©coe can be selected for example; 01-3 alkyl hydrogen. in certain embodiments; Each + is a hydrogen and an alkyl group has the structural formula 611-6112-. Yo "AlkoOXy " refers to the —OR group where R is an alkyl as defined herein. Examples of alkoxy groups include methoxy ; ethoxy; 1- propoxy « ISOPropoxy ; And 1-butoxy A. butoxy certain embodiments; the de sens alkoxy is alkoxy « C1-6 alkoxy » C1-8 alkoxy 01-4; and in certain embodiments; .C1-3 alkoxy ONEY

VE

to a single moiety of a branched unsaturated hydrocarbon group “alkyl” The term “alkyl” of 01 atoms refers to 1 carbon atom; from Te to 1 Bah for example from ALLL or straight to * atoms of carbon. 1 to ; atoms of carbon; or from 1 to + atoms of carbon; of 1 carbon" From It will be realized that a supersaturated alkyl has a minimum number of © carbon atoms. is © litweb-1 ¢is0—propyl iso-propyl ¢ Propyl dus yn alkyl groups on methyl; ethyl” lycid-1 hexyl lesch-1 » tert-butyl tert-butyl “iso— butyl; ‎ 02-4 alkyl « alkyl at least. carbon atoms ? polycyclic in certain embodiments; the cycloalkanediyl group is C3-8 03-12 cycloalkanediyl “cycloalkanediyl 03-6” and in m a sample. C5-6 Lcycloalkanediyl 1 Examples of cycloalkane diyl groups include cyclohexane-1; 4-diyl cyclohexane—1,4-diyl ; cyclohexane-0” ?-diyl cyclohexane—1,3—- .cyclohexane—1,2-diyl ; and 0-7-diyl cyclohexane refers to the mono-radical group of a monomeric saturated hydrocarbon “Cycloalkyl” The term “cycloalkyl” refers to 12-63 Cycloalkyl or polycyclic. in certain embodiments; The cycloalkyl group is C5-6. Cycloalkyl; and in certain embodiments; 03-6 Cycloalkyl; Such as gh alkane or potassium "5" sulfur sulfur "0" Oxygen 'N' Nitrogen '. 0 Potassium

ONEY

A —_ _ in certain embodiments of hydrocycloalkane diyl; The heteroatom is selected from !a and 0. Compositions of polythio (Ji) terminated with thiol hardens having extended service life are disclosed. In these systems the poly-epoxy hardener is protected or microencapsulated and dispersed in the formulation containing a thiol-terminated polythioether and a base catalyst. when exposed; eg © for example; to high temperature and/or mechanical stress; The polyepoxy is released from the encapsulating material and reacts with the thiol-terminated polythioether to form a solidified composition. in certain embodiments; These systems provide an operating life greater than YE hours at least. Encapsulated Curing Agent alae Compositions offered by the present disclosure include an end-ended poly of ether (Jaf); an epoxy-encapsulated poly-0 curing agent; and a base catalyst. One-part formulations have a working life of YE aly. “at least hours” ? at least days; at least one week; at least two weeks; and, in certain embodiments, at least weeks. The service life refers to the time during which the composition remains workable so that the composition can be applied to seal surfaces tightly. Can be fired Polyepoxy hardener from packaging product upon application of an elevated temperature V0 mechanical voltage and/or ultrasonic treatment At release from sale packaging the polyepoxy hardener reacts with thiol-terminated polythioethers to form a formulation .cured sealant Polyepoxy curing agents can be encapsulated in a microencapsulation as a solution or be retained in a porous substrate such as yellowish encapsulant materials .matrix encapsulant materials Yo .coated polyepoxy resins are described as JE In ref. Yuan et al., Polymer Degradation and Stability, 2006, 91, 2300-2306; Blaiszik et al., “Jin et al., Polymer, 2011.12.005 5” Polymer, 2009, 50, 990-997 and are used in self-hardening polymer systems. Micro-coatings containing epoxy resins such as Epon® 815C and Epon® 828 can be prepared via in situ polymerization.

For urea-formaldehyde 0 (UF) urea-formaldehyde microspheres can have a diameter eg JB from about 0.100 µm to about 700 µm Sie from about 151 µm to about You can micrometer or other dimensions Micro-encapsulated epoxy composites are commercially available and include “all 2” (Lipo Technologies) LT-81380© flour; hexane or dissolved in .aqueous solvent jl For also aerospace leakage applications the epoxy can be released from the microspheres by exposure to high ha degrees and/or mechanical energy This can include voltage mechanical, for example, impact force, shear force, “grinding force” and/or ultrasonic force. Less than about 50°C; Less than about 71°C; Less than about 880°C; and in certain embodiments than about 100°C. s epoxy at low temperatures but above room temperature. The temperature of the DULY (for example, JED) can be determined by the chemical composition Vo of the polymeric matrix. The rate at which the sealing composition hardens after the release of the epoxy hardener from the microcasings can be determined by the temperature of dispersion of the microcasings Examples of epoxy compounds suitable for use in sealing compositions offered by the present disclosure include, but are not limited to, poly-epoxy compounds, Jie hydantoin diepoxide, and diglycidyl ethers 0 A- bisphenol Epon® 828 (Resolution Performance Products, LLC) Diglycidyl ether bisphenol F-bisphenol Novolac® epoxide compounds such as 438 DEN® (available from The Dow Company) Certain unsaturated epoxide-treated resins; and mixtures of any of the above. In certain embodiments; polyepoxy comprises a reactive resin that is an acid-based polyepoxy yo dimer As indicated” (eg

“yam” in certain embodiments; Certain hardening agents include .00005/07771171 in Publication 5.No. No. bisphenol bisphenol diglycidyl ether hydantoin diepoxide; Glycidyl diglycidyl ether (gla) (Resolution Performance Products, LLC) Epon® 828 as Dow (DEN® 431 as Novolac® bisphenol-A ether; Epoxy-type compounds epoxidized unsaturated phenolicresins phenolic resins (Plastics©) embodiments of dimer acid-based epoxy resins; acid-based epoxy dimer resins

Youu rhombus to 001 given; The polyepoxy hardener has a molecular weight of about dalton to about fon dalton; from about 100001 Daltons to about Yoo Daltons; from about .0001 Daltons to 5000 Daltons; and in certain embodiments of about 0 the term polyepoxide refers to a compound having two or more reactive epoxy groups or a combination thereof. Vo in certain embodiments; A poly-epoxy hardener comprises a prepolymer having an epoxy functional group. Examples of prepolymers having a suitable epoxy functional group include polycomponents in US Patent No. le having an epoxy functional group disclosed dls and polythioethers having an epoxy functional group disclosed in patent 1/5, US No. 7,171,155. in general; when used as a hardening agent; A prepolymer has 1 Dalton; less than about 010,000 epoxy functional groups with a molecular weight of less than about 500 Daltons; and in certain embodiments; less than about 1,000 Daltons; less than about 1 0 7 daltons by weight to about 7 1.5 in certain embodiments; Contains an epoxy hardening agent of approx. by weight; from about 7 7 wt to 7 01 wt to about 1 7 wt of formula; from about 0 given incarnations; From By about 8 7 wt.; from about 7 7 wt to about 7 76 wt; from about 3 wt to about 7 © wt; Where 7 by weight is based on the total solids weight in the formula.

Thiol-terminated polythioethers Examples of polythioethers with a thiol functional group are disclosed; For example, in US Patent No. 1,177,179. in certain embodiments; The thiol-terminated polythioether polymer comprises Permapol® P3.1E. Available from: M International Inc., Sylmar, CA [0]40-085010. Other examples of thiol-terminated polythioethers are disclosed in US Patent Publication No. SYN ena in certain embodiments; A polythioether with a thiol functional group includes: 0 main chain with the structural formula: (1) (V)-R1-[-S—(CH2)2-O-[-R2-O-Jm—(CH2) (2-S-R1]n- aa 00 (1) All 41 are independently selected from the Nn 02-10 alkanediyl group — “alkanediyl 03-6 branched group. e cycloalkanediyl group 06-8; 06-10 cycloalkanediyl group; cheterocyclic heterocyclic group —[(-CHR3—)s—X-]g—(CHR3)r— where each R3 is selected of hydrogen and methyl; (1) 1 each R2 is independently selected from: “C2-10 n-alkanediyl group 03-6 alkanediyl branched dc seas group” C6-8 cycloalkanediyl “C6-14 alkanecycloalkanediyl heterocyclic group; group -0112-)]- ¢)s—X—]q—(CH2)r— XK (7) is independently selected from R6 Cua “—NR6— ic gana SO chosen from 1 0 and a methyl group ¢ (4) ranging from 0 to 0 5; (°) 0 is an integer from 1 to ha ONLY yy is an integer from ? to 6; 5 (6) to ©; and 1 is an integer from 0 (VY). 01 is an integer from ? to aT (4) in certain incarnations; The thiol-terminated polythioether includes a polythioether-terminated polythioether (oY) _buthiol selected from the thiol-terminated polythioether of formula © the thiol end of formula (?a); and a combination thereof: (Y)HS-R1-[-S—(CH2)p—O—(R2-O)m—(CH2)2-S—-R1-]n—-SH (I }{ HS-R1-[-S—(CH2)p—O—(R2-O)m—(CH2)2-S-R1-]n-S-V''-}zB : selected independently from RT every 0 02-10 alkanediyl, 06-8 cycloalkanediyl, 66-14 alkanecycloalkanediyl, f-a(-3a-)-and[-5-2(-43a1a-)]- where: « 5- 8 heterocycloalkanediyl

VAY is an integer from 5 © to 1 is an integer from 9 ;01 is an integer from ? to » VO is selected independently from hydrogen and methyl; and R3 each is selected from hydrogen (R is independently selected from -0-) (-5-) and -value-” where X is each methyl: is independently selected from R2 each

SAEY

» C1-10 alkanediyl, 66-8 cycloalkanediyl, 66-14 alkanecycloalkanediyl and R are according to their designation for “R3 where y and “e”—[(-CHR3-)s—X-]q—(—CHR3- )r— 4 ¢R1 00 is an integer from zero to am la to 1 is an integer from 1 5

m is an integer ranging from VAY 8 denoting a core of 2; A polyfunctional operator ending in kenyl B(-V)z 2 is an integer ranging from ? to 1; and

0 each V is a group that includes a terminal qunyl assembly; And every -1/”-- is derived from the reaction of -1/ with a thiol. In certain embodiments it has the form (1) and the form ((I 1+) is -a(0112)-0[-5-2(-0112-)]v where 5 is 7; 7 is -0-,; 0 is 1 17 is 7 2 is ethan gh yl ethanediyl » 00 is 7 and 7 is A

Vo in certain embodiments has the formula ( ) Y and the formula ( R1 ( I ) is chosen from the C2-6 diyl alkane —~[-(CHR3)s—X-]q—(CHR3)r —, in certain embodiments has the form (7) and the form (?a); 1 is —[-(CHR3)s—X-]q- ((CHR3)r— and in certain embodiments X is -0- and in certain embodiments, X is -5-. In certain embodiments it has the form (7) and the form (?a), where RI is —[-(CHR3)s—X-]q-

“(CHR3)r- 1 5 is rey is q “Y is 3 Xs is”—S— in Aza embodiments where m is 0 . rey is 31 Xs is -00)-; And in embodiments (Axa 5 is rey is q «Y is 3 Xs is -0)-.

‎OALY

_\¢ —_

In certain embodiments it has the form (7) and the form oY) where RI is —[(CHR3)s-X-1q—

((CHR3)r- all 43 are hydrogens; and in certain embodiments, at least one 43

is methyl .

In certain embodiments it has the form ( ) Y and the form ( I ) all R1 is the same and in certain embodiments;

© 81 At least one is different.

Various methods can be used to prepare thiol-terminated polythiocomplexes (fu) of the formula ()

and formula (7a). Examples of suitable thiol-terminated polythioether polymers are described; and knock

to produce it; In US Pat. No. 1,177,179 at column 7; line 75 to column ;; line

"?; column 7 line FA to column 10; line £00 and column (VY) lines © to column 17 0 line YY where the parts mentioned are included here for reference. die can be compounds

Polythioethers terminated with the aforementioned di-functional thiols; In a more specific sense

linear polymers with two terminal thiol groups; or multiple functional groups;

In a more specific sense, they are branched polymers with three or more terminal thiol groups. If compounds

Suitable thiol-terminated polythioethers available plat as JB as “Permapol® P3.1E 1” from PRC-DeSoto International Inc., Sylmar, CA.

Suitable thiol-terminated polythioethers can be produced by the diquinyl reaction

fi or mixtures of diethyl ether with an excess of dithiol or mixtures of di-compounds

thiol. For example, JE, DJs compounds suitable for use in the preparation of polythio compounds

Dithiol-terminated ethers (those of formula oT) include other dithiol compounds 0 disclosed herein or combinations of any of the dithiol compounds disclosed herein.

In embodiments of (Alma) dithiol has the structural formula: (Y).

(*) HS-R1-SH

Where:

ONLY

C \ — 1+ is selected from:

C2-6 alkanediyl, 66-8 cycloalkanediyl, 66-10 alkanecycloalkanediyl, ¢—[-(CHR3)s—X-]q—(CHR3)r— , 05-8 heterocycloalkanediyl R3 JS© is independently selected from hydrogen methyl; Each X is chosen independently from -0- ( -5-); f-ann- where R is chosen from hydrogen and methyl; is an integer from AY 1 9 is an integer from 1 to ©; And 1 001 is an integer ranging from ? to He in certain embodiments of a dithiol with formula ( ) RI is -0(01143)- and [-011143(5-2)-]-. in certain embodiments of a compound of formula (7); X is selected from -0 and -5,; So -]- (CHR3)s—X-]q—(CHR3)r— in the form (¥) is —[(-CHR3—)s—O—]q—(CHR3)r— or —~[(-CHR32-)s—-S-]q—(CHR3)r- In embodiments of Fg 5 Alma are equal e.g. Yo for example Laie Cua is 5 and two together. In Certain embodiments of dithiol of formula (9) RI are chosen from 62-6 —[-(CHR3)s—X-]q—(CHR3)r— ; alkanediyl in embodiments of R1 (dime is —[-(CHR3)s—X-]q—(CHR3)r— and in certain embodiments X is —0O-— and in certain embodiments X is —S—

-?1- In certain embodiments where RI is [-(CHR3)s—X-]Jg—(CHR3)r— 5 is 17 01 is 7 9 is Xe) is “— S—in embodiments of dua (Ame 5 is oY is oY a is or is “—0O— and in embodiments (Ame 5 is oY = oY is Xe) is —0O- in certain embodiments Rl dus is -(01143)-and [-43(5-2a001)-]- all R3 is © hydrogen; in certain embodiments at least one R3 is methyl Examples include gh old suitable thiols, eg gh OBEY OO JB thiol 0 1 ethanedithiol 7-propanedithiol 0 1 propanedithiol 7-propanediyol Vode "-butandithiol 0 150180601101 -butandaithiol; ?-methylbutane; (gla dipentenedimercaptan; Ji) ethylcyclohexyldithiol (ECHDT) dimercaptodiethylsulfide; substituted with dimethylmercaptodi methyl-dimercaptodiethylsulfide “ has a dimethyl substitution mercapto-diethylsulfide; dimethyl-dimercaptodiethylsulfide; dimercaptodioxaoctane (lao”) “dimercaptodioxaoctane dimercapto-7-oxapentane” and a combination of the above. A polythiol may include one or more groups attached to a carrier selected from an alkyl group (lo (ex. 61-6); ic gana lower alkoxy; a hydroxyl group comprising alkyl groups attached to a suitable carrier; For example, (Jad) 61-6 linear alkyl 0 amalgams » C3-6 branched alkyl; cyclopentyl and cyclohexyl .examples include gh ole gal thiol gh Aube mercapto gh ethyl sulfide dimercaptodioxaoctane (DMDS) (in formula (¥)” Rl is —[ (-CH2-)s—X-]g— (((CH2)r— where 5 is 1 7 is 7 0 is Xs) is:(-5-dimercaptodioxaactane (DMDO) ) dimercaptodioxaoctane Yo (in the formula (¥) Rl is—[(-CH2-)s—X-]q— ONLY

-11- mercapto glo a1 and is -0-); Xs 7 aT 7 is 0 YF where 5 is ((CH2)r— -])-0112-(5-76- -7 -Axapentane 080601808 ) in the formula (¥(¢ 41) is dimercapto and is -0-). It is also possible to use 1 is GY AT 7 -©(0112)-109; Where 5 is the one that includes both heteroatoms in the main carbon chain Jab gla compounds that Jie methyl groups. Includes JE and alkyl groups fixed on a carrier; For example ©

HS- eg die is replaced by DMDS (JE eg Tabkarmala

HS-CH(CH3)CH2-S-CH2CH2-SH «CH2CH(CH3)-S-CH2CH2-SH

HS—CH2CH(CH3)-S— eg “dimethyl substituent with dimethyl” DMDS HS—CH(CH3)CH2-S-CH2CH(CH3)-SH y CHCH3CH2—-SH and fi- ) suitable for the preparation of polythio-divinyl compounds include divinyl ethers 0 (divinyl ethers ji), for example; diquinyl compounds fi) added polythio(£) (¢£)CH2=CH-O—(-R2-O—)m-CH=CH2 03-6 ; The 02-6 n—alkanediyl group in formula (4) is chosen from the R2 group where C6-10 is a branched CO6-8 cycloalkanediyl group; alkanediyl group 10 f-a(-0112-)-0[-5-0(-0112-)]-; where 5 is an integer :alkanecycloalkanediyl to 5 and 3 is an integer ranging from ?1 ranging from ? 0 to 7 is an integer ranging from is R2 »(4) of the formula A divinyl ether in certain embodiments of divinyl ether to 01. branched; group 03-6 branched alkanediyl -02 6); group n—alkanediyl group and in embodiments alkanecycloalkanediyl 06-10 06-8; cycloalkanediyl group Y —[(-CH2-)s—O-]q—(—CH2—)r— iis suitable; For example; Compounds with divinyl ethers including at least 1 to 1 divinyl ether compounds; For example of the oxyalkanediyl oxyalkane diyl group the formula (;) is the number of AM compounds where dyad yl; meaning more gla; Oxyalkan

M1- True ranges from 1 to ;. in certain embodiments; The formula AM (;) is an integer ranging from " to nt. It is also possible to use commercially available diphenyl ether mixtures an with an average non-integer value of the number of diyl oxyalkane units per molecule. Thus; 77 in the formula ( 2) It can take a rational numeric value ranging from zero to Vee for example JE from 01 to 01 ge 0 to 4.0 or from 0.0 to He

Examples of suitable divinyl ether Jy compounds include; For example (JB) ethylene glycol (EG-DVE) in formula (4) is my ethanediyl 1); butane diol Divinyl (R2) (BD-DVE) butanediol divinyl ether in formula (4) is mj butanediyl dibutane (0 is 1) Jud hexanediol divinyl ether R2 ) (HD-DVE) in formula (;) is (my hexanediyl) 1) diethylene glycol divinyl ether (R2) (DEG-DVE) diethylene glycol divinyl ether ji) in

The formula (£) is ethane diyl (ms ethanediyl is 1)”; triethylene glycol compound Vo Di Jus divinyl ether (42a in formula (4) is ethanediyl My is?); Tetraethylene glycol (R2) divinyl ether (R2) divinyl ether with the formula (£) is divinyl ether (£) cyclohexanedimethanol divinyl ether; Polytetrahydrofuryl divinyl ether; Jud trivinyl ether le monomers Y. eg lp methylolpropane trivinyl ether; monomers ether monomers ji have four functional groups; for example, pentaerythritol tetravinyl ether; and mixtures of two or more of these Jud polyvinyl ether monomers. Poly Jud polyvinyl ether one or more of

-?and 1- Groups fixed on a carrier selected from (JS) hydroxyl groups, hydroxyl groups, calkoxy groups, and amine groups in embodiments of Gls dime di Jud ether where 42 is in the formula ( ;) is a branched 03-6 alkanediyl that can be prepared by reacting a polyhydroxy© compound with acetylene Examples of diphenyl ethers of this type include compounds where R2 of the formula (;) is a group methanediyl has an alkyl substitution eg -(011)0113- (eg Pluriol® blends eg Pluriol® E-200 Diquinyl Ether Compound (BASF Corp.) being 42 in formula ( 4) is an ethane-diyl and 71 is an alkyl-substituted SYA ethane-diyl (eg -(0112011)0113- eg 0 DPE polymeric mixtures including DPE-2 Ro .) International Specialty Products (DPE-3) Other useful didecynyl ether compounds include compounds where 42 in formula (4) are polytetrahydrofuryl (THF= or polyoxyalkanediyl “eg example those out there average about ? .monomer units Kay Vo The use of two or more types of polyvinyl ether monomer jij Jud has the formula (4). Subsequently; in certain embodiments; Two dithiols of formula (©) and a polydienyl ether monomer of formula (©) can be used; one dithiol of formula (©) and two polyvinyl ether monomers of formula o£) and two dithiols of formula (¥) and two dithiol monomers of formula (;); and two or more compounds of one or each Yo of formula (©) and formula (£) to produce a variety of thiol-terminated polythiol ether compounds. In certain embodiments the polyvinyl ether monomer comprises from 0 to less than Zon per mole of pind reactants For the preparation of thiol-terminated polythioethers; and in certain embodiments; 30 to less than 0 7 mol. ONLY

1 in certain embodiments provided in the present list; Relative quantities of dithiol ether compounds are selected to obtain polythiol ether compounds with terminal thiol groups. Jud gla and compounds thus; A dithiol of formula (7) or a mixture of at least two different dithiols of formula (3) is reacted with a diphenyl ether of formula (;) or a mixture of at least two different Jie-components Diquinyl ether compounds having the formula (;) in reactants ©

Yoo to 1 : 1 i.e. 1 : 1 molecular of thiol groups to thehenyl groups greater than

De The reaction between dithiols and diquinyl ethers can be catalyzed by a free radical catalyst. Azo 820; For example (JD) suitable free radical catalysts include eg azo(bis)isobutyronitriles cazobisnitriles eg azobisnitriles organic peroxides over tazo(bis)organic oxides isobutyronitrile (AIBN) ¢ t-butyl peroxide and 1-butyl benzoyl peroxide benzoyl peroxide Jd can be hydrogen peroxide and inorganic peroxides such as hydrogen peroxide; or ultrasonic irradiation ionic catalyst An ionic catalyst is an iad crack catalyst in certain embodiments; the catalyst does not include acidic or ultraviolet radiation Vo basic compounds; and does not produce acidic or basic compounds upon decomposition. Examples of free radical catalysts include a catalyst » (Du Pont) Vazo®-64 «(Du Pont) Vazo®-57 type Azo for example

V-65B® (Meldal Row Specialty Chemicals) /-70© (Du Pont) Vazo®-67 Examples of other free radical catalysts are per alkyl oxides (Wako Specialty Chemicals) t-butyl peroxide can be ; eg ;-butyl alkyl peroxides 0 Reaction by irradiation using ultraviolet illumination with or without cationic starting fraction . At least one compound has formula (7) and at least one compound has formula (;) followed by the addition of a residual degree; on 1071 degrees Celsius to 100 masked catalysts” and conducting a reaction at a temperature of YO A

— \ \ —

eg 71°C to 900°C; dad time from? to ; ? hour; for example

the metal? to 6 hours.

According to what has been disclosed here, the thiol-terminated polythioether compounds may include a compound

Polythioether has multiple functional groups; meaning; The average can include functional groups

© over 7.0 includes thiol-terminated polythioethers having several functional groups

suitable; For example; Those with the female form (*):

0 8)-4- 2

where A (1) includes, eg (JB) structural formula (1); Ju 8 (V) has an equivalence unit of 2

for a multi-functional worker; and (7) 2 has an average value greater than 0.; And the; in certain > embodiments; between value VV value between ? And the; A value between TeV and in (Ame) embodiments is an integer

ranges? to 6.

It includes agents with multiple functional groups suitable for use a in the preparation of thiol-terminated compounds

multi-functional groups agents with three functional groups ¢ viz.; compounds where 2 is 8

Three-group fit operators include Ayala ll for example; triallyl cyanurate “Y”) driallyl cyanurate (TAC) 00 7-propanetrithiol; tri vehicles

trithiols contain isocyanurates; and gia moods as shown in

U.S. Patent Publication No. 171 L .. / Yel ¢ The portion cited herein is included for reference.

Other useful polyfunctionalizing agents include:

trimethylolpropane trivinyl ether ji) and poly-0. polythiols described in US Patents No. 11.17; 51:5,17;f

0, Y YO, EYY . Mixtures of agents of multiple functional groups can be used.

as a result; The thiol-terminated polythioethers are suitable for use in embodiments

Presented by the present disclosure can include a wide range of average functional groups.

For example; Three-functional agents can carry an average of functional groups

_— \ \ _ From 7.05 to oF eg from 7.1 to 7.1. A wider range of average functional groups can be achieved by using multifunctional agents quadruple or higher. Functional groups can also be implemented by factors such as stoichiometric quantity as understood by those skilled in the art. Pthiol-terminated polythioethers having a functional group greater than Yor© can be prepared in a manner similar to the dithiol-terminated polythioethers described in US Patent Publication No. 10 / RRR RRE . in certain embodiments; Polythioethers can be prepared by combining (1) one or more of the dithiol compounds described here with (7) one or more of the didecynyl ethers described here and (©) one or more multi-functional group agents. That reaction of the mixture; optionally in the presence of a suitable Jae; to yield 0 to obtain a thiol-terminated polythioether having a functional group larger than Nov JL In certain embodiments; the thiol-terminated polythioether includes the reaction product of the reactants which They include: (a) a dithiol with formula (3): 45-81-90 (*) where: +1 is chosen from: C2-6 alkanediyl, 06-8 cycloalkanediyl, 66-10 alkanecycloalkanediyl, 65- heterocycloalkanediyl , 8 ¢—[-(CHR3)s—X-]q—(CHR3)r—, where: R3 JS Ys are independently selected from hydrogen and methyl; each X is independently selected from O— -58-); “NH- and -4Al- where R is selected from hydrogen and methyl;

is an integer from AY 1 is an integer from 1 to *; and r is an integer from 10 to 0; and (b) a compound didecynyl ether with formula (4): (£)CH2=CH-O-[-R2-O-]m-CH =CH2 0 where: each +2 is chosen independently from: C1-10 alkanediyl, 66-8 cycloalkanediyl, 26-14 alkanecycloalkanediyl 5 — dua “[(-CHR3—-)s—X-]q— (-CHR3—)r- and » and C and O are as specified above; m 001 is an integer ranging from zero to $0 0 is an integer ranging from 1 to FRAX m is an integer ranging from ? to 6. In embodiments of (Axa) (z) Je lal materials include a polyfunctional compound such as polyfunctional compound B(-V)z » where s —V and 2 are as specified herein. Vo The thiol-terminated polyether compounds presented in the present disclosure Jia The thiol-terminated polythiol ethers have a molecular weight distribution. in certain embodiments; The thiol-terminated Sl-polythiocompounds exhibit an average molecular weight number ranging from 500 Daltons to 5000018 Daltons; in certain embodiments; from 50,001 Daltons to 6 Daltons and in certain embodiments; From 0001 Daltons to 0010 Daltons. in certain embodiments; The thiol-terminated polythioethers sade Yo exhibit many degree of dispersion tMW/Mn) average molecular weight/average weight number (all ONLY)

1

ranges from 1 to ye and in ime embodiments from 1 to 5. Weight distribution characteristics can be specified

Molecular composition of thiol-terminated polythioethers by gel permeation chromatography.

fixtures

in certain embodiments; The compositions presented in the present disclosure include (a) thiol-terminated polythioethers; (b) epoxy coated polyurethane; and (c) an amine catalyst. It can be terminated polythioether

The thiol tip is any of those disclosed here and can be epoxy-coated polyurethane

Epoxy encapsulated in a polymeric binder which is then encapsulated again in a polymeric binder.

In dime embodiments the amine catalyst may be a tertiary amine catalyst. Examples include

suitable triamine catalysts; For example :

0 No L-11dimethylethanolamine (DMEA) N,N-dimethylethanolamine diaminobicyclooctane “(DABCO) diaminobicyclooctane triethylene (TEDA) diamine bis( 7- Dimethylaminoethyl)2-515 (BDMAEE) dimethylaminoethyl)ether [1-ethylmorpholine « 1l-1-dimethylpiperazine ¢ lal thla ‘no GN methyl-di

yad-1l (PMDETA) pentamethyl-diethylene-triamine amine shim oll) 1 methyl yad-1l (N (DMCHA) dimethylcyclohexylamine methylcyclohexylamine .no-l-1-dimethylethylene Amine (DMBA) dimethylbenzylamine benzylamine -dipropylene-triamine die BN” (N77 Lal Lal Thala “dimethylcethylamine” triethylamine “pentamethyl-dipropylene-triamine (PMDPTA)

V5 0 -(7-hydroxypropyl)imidazole 1=(2-hydroxypropyl) imidazole Other suitable amine catalysts include eg tetramethyguanidine (TMG) jie cyclonone (DBN) dizabicyclononene diazabi cyclo ondecine

(DBU) diazabicyclo undecene and imidazoles; and ebicyclic guanidines (eg vo) -triazabae cyclo

e01" [0..; edis-*-in and 1,5,7,-118285107010]4.4.0[1066-5-908 7- (TBD) Gli ov 5 0 methyl azapae cyclo[1] ,4,;edes-*-ene” 7-methyl-,1,5,7 (MTBD) triazabicyclo[4.4.0]dec-5-ene (TBD) in certain embodiments; an amine catalyst chosen from DABCO (DBU) and mixtures thereof. 0 _ Compositions may comprise one or more different types of amine catalyst. In certain embodiments; compositions given by disclosure include a plus a thiol-terminated polythioether; or a reaction product of Any one of the reactions described herein or a combination of any of the above; one or more product of addition reactions containing thiol-terminated sulfur 1101 and/or prepolymers 060017/00©35. ) containing 0 thiol-terminated sulfur and/or a prepolymer is any polymer having at least a sulfur sul;atom in the repeating unit; including, but not limited to, thiol polymeric compounds polymeric thiols poly(sb) thioether compounds; polythio-Si compounds; polyformals; polysulfide compounds. polysulfides, and the term "ol" according to its use here refers to a compound that includes a thiol group or two compounds (cmercaptan), meaning; 0 “SH” group either as the sole functional group or in combination with other functional groups; For example hydroxyl groups as is the case; eg (Jal) thioglycerol compounds 10109:7080:5. The term polythiol refers to a compound having more than one SH group; eg a dithiol or a thiol with a higher functional group. Such groups are usually terminal and/or attached to Alla is a substance that contains an active hydrogen atom 0 that is reactive with other functional groups.According to usage cla, the term "polysulfide" refers to any compound containing a sulfur-sulfur-sulfur linkage (-5-5-) A polythiol can include both a terminal sulfur and/or a fixed carrier (SH) pendant sulfur and a non-reactive sulfur atom —S— (non-reactive sulfur atom or -5-5-). Subsequently; The term polythiols generally includes polythioethers and polysulfides. Examples of polymers containing additional YO sulfur useful in the formulations presented in the present disclosure include; For example; that is

— a \ — cited in US Patent No. RPE HAVA ES MEE; and 0.077; In US Application No. LY ALY TY certain embodiments the compositions given in the present disclosure include a polythioether having the structural formula: -0[-41a-0112(2-5)-0[-42-0-]-0112( 2-0)-5-]-41a-0 where 81 is chosen from

C2-6 alkanediyl, 66-8 cycloalkanediyl, 66-10 cycloalkylalkanediyl — where —[(-CH2-)s—X-]q—(-CH2—)r— 5 «—[(—CH2-)s —X-]gq—(-CH2—)r— « : at least one has a methyl group substituted; 2+ is chosen from CH2- and -)]- « 22-6 alkanediyl, 06-8 cycloalkanediyl, 06-10 cycloalkylalkanediyl X¢CH2-)s—X-]g—(-CH2-)r— 0 is selected from 0; 5; F-45Al1-” where RS is selected from hydrogen and methyl; 177 is an integer from zero to AN Oe is an integer from 1 to ape an integer from ? to 6; 0 is an integer ranging from 1 to © and is an integer that offsets from ? to .01 such polythioethers are described in US Patent No. 1,177,179 at column oF line 75 to column of line JE fe 15 that one or more additional copolymers containing disulfide or multi-functional groups; For example it has from © to 76 terminal groups; or a mixture thereof. in certain embodiments; Compositions given by the present disclosure include from about 7 01 wt. to about 0 wt. of a sulfur-containing polymer offered in accordance with the present disclosure; from about 01 A wt to about 7 880 wt” from about 7 710 wt to about 7 1710 wt; and in 0 certain embodiments from about Er 7 by weight to about colo 7 Te where 7 by weight relative to the total weight of all non-volatile constituents of the formulation ine (dry weight). According to usage cla, the term polysulfide refers to a polymer containing one or more disulfide bonds; In a more specific sense, links -[5-5]-; in the main polymer chain and/or at the ONEY positions

attached to a carrier in the polymer chain. in certain embodiments; The polysulfide polymer will contain two or more sulfur-sulfur bonds. Commercially suitable polysulfide compounds are available for example from Akzo Nobel and Toray Fine Chemicals under the brand names Thiokol-LP and Thioplast®. Thioplast® products are available in a wide range of molecular weights ranging from ; For example; From less than 0101 to more than Aver with a molecular weight is the average molecular weight number in g/mol. in some cases; Polysulfides have an average molecular weight number of 0.001 to ev ve. The crosslink density of these products also varies depending on the amount of crosslinking agent used. The -SH content can also vary meaning more specifically the content of a thiol or two compounds. The vehicle content and weight

0 The molecular weight of polysulfide can affect the rate of hardening of the polymer as the rate of hardening increases with increasing molecular weight. Polyformal prepolymers useful in aerospace sealing applications are being disclosed; For example in US Requisition Publication No. 00107/07747605 and US Requisition Publication No. 010117781

0 in certain embodiments; The sulfur-containing polymer is selected from polythioether and polysulfide; and combination thereof. in certain embodiments sulfur-containing polymer including polythio (Age gi) certain embodiments; A sulfur-containing polymer that includes polysulfide. A sulfur-containing polymer may comprise a mixture of different polythioether and/or polycandle compounds and the polythioether and/or polysulfide may contain the same or different number of functional groups. in certain embodiments; He is

7 ;; From IY to eT for a medium sulfur-containing polymer with functional groups ranging from 0 to 7 to 1,5. For example; A polymer containing 7.05 to ? and in certain embodiments; on sulfur from a polymer containing sulfur d-functional groups; and three functional groups; and their combinations. Characteristics Q

l

m for aerospace applications; It is desirable that the sealant meet the requirements of 1/11-5-224735 ail) Sealant Class C) with a curing thickness of #50 mm; It shows an elongation greater than 77090; It has tensile strength greater than 1.77 MPa, excellent fuel resistance and retains these properties over a wide temperature range from 01°C to YAY°C. in certain embodiments; A hardenable formulation can have a service life of ? days at least; and in certain embodiments; ; at least weeks at about Yo °C. in certain embodiments; Polyepoxy 001760077 may be released from sale packaging upon application of thermal and/or mechanical stress for less than 1 second; less than about 1 minute; or less than about Y minutes. The release temperature can be higher than about 50 °C; from about Ve 0 degrees Celsius; and in certain embodiments; higher than about 90°C. in certain embodiments; Release temperature from about 0°C to 0010°C; Av °C to 001 °C; and in certain embodiments; From 90°C to 171°C. High heat can be shed with a radioactive source; For example (JB) infrared heater; machine heated; or by induction heating. High heat can be applied to exposed surfaces of the Vo-sealing ile composition or to the jointed surface sealant. Involves mechanical stress; eg (JE Impact, shear, crush, ultrasonic exposure Polyepoxy can be released from a microcasing by shear forces by dalling the surfaces Polyepoxy can be released from the cabal sald by impacting the combined surfaces with the sealant applied to them In addition, in embodiments ime ultrasonic radiation can be used to tear the sale 0 packaging to release the polyepoxy eg JB ultrasonic radiation can be directed at the sealant and/or surfaces to which the sealant is applied on it for a sufficient period at an appropriate frequency to release the polyepoxy from the microfilaments.Formulations: Lacquer

—vq- The compositions offered by the present disclosure may include one or more components suitable for use in aerospace seals and depend at least in part on the desired performance characteristics of the hardened sealant under conditions of use. In embodiments certain; Compositions offered by the present disclosure include one or more enhancers from 7 15 wt. to 7 0.1 adhesion. One or more additional boosters can be present in an amount of 5 by weight; 7 1 certain embodiments; less than As of 5 7 wt; Less than 7 7 by weight; JB formulation; Based on total dry time of formulation. Examples of adhesion enhancers include phenolic compounds and “Methylon® phenolic resin”; For example; phenolic resin containing silane group; for example organosilanes organic silanes such as amino functional or amino functional; mercapto; Mercapto epoxy Epoxy 0 or 1100-8 ©51100651. Other useful adhesion enhancers (51100651© A-187 Jt) are known in the art. The formulations offered by the present disclosure may include one or more of various types of suitable materials such as are generally known in the art; Including fillers. Filling materials include carbon black JE; For example, inorganic fillers inorganic fillers Vo silica powders Silica ((CaCO3) calcium carbonate black Jdightweight fillers and lightweight fillers include ¢ polymeric powders Those disclosed in the JB Patent are suitable lightweight fillers; 01 by weight to 7 01 of filler or a mixture of fillers; from 7 70 by weight to 7 46 by weight, based on the total dry weight of the formulation. present one or more colourants, fire retardants, accelerators, thixotropic agents, masking agents, solvents, adhesion promoters, adhesion retardants, or a combination of any of the above. As you will realize, masking agents Yo

to

additives used in combination to be compatible with each other as well as the polymeric component;

hardening agent and/or the catalyst. In dime embodiments the compositions offered by the current disclosure include low AEG ede particulate matter. According to usage cla the low density; FLY when used with reference to such particles means that the particles have a specific gravity of no more than 58 in certain embodiments and in certain embodiments; no more than 0.1 . Suitable lightweight fill particles often fall into two categories - microspheres and amorphous particles. The specific gravity of microspheres ranges from 1.1 to 1.7 and includes; For example; Poly Yo Styrene foam. polystyrene microspheres of polyacrylates and polyolefins; silica microspheres having particle sizes from © to 100 µm and a specific gravity of ©0.7; (© 16165 AD 500050). Other examples include alumina/silica microspheres with particle sizes in the range from © to 700 µm and a specific gravity of CL. Oly So (Fillite®) aluminum silicate microspheres have JE type of about dE GUS ((Z-Light®) ov Jim J ego Ye of polyvinylidene copolymer coated with calcium carbonate of 0.11 specific gravity. (Dualite® 6001AE) Microspheres of acrylonitrile copolymer coated with Dualite® E135 Jiscalcium carbonate have an average particle size of approximately 6 μfe and a density of 0.175 g/cm? (A160/48). YS fillers suitable for reducing the specific gravity of the composition, for example JB hollow microspheres Je Expancel® microspheres (available from AkzoNobel) or low density polymer microspheres Dualite® (from (Henkel) in certain embodiments; the formulations presented in the present disclosure include lightweight filler particles having a film-coated outer surface; for example, those described in US Patent Publication No. 4 178749 7000/00; where the part is included

Yo _mentioned here for reference.

“yy in certain embodiments; Includes low density fill material less than 7 7 wt. less than by weight; Less than 0.8 7 wt» Less than 7 .78 wt; ; less than 7 0.1 wt.; less than # 5 by weight and in certain embodiments; less than 0.58 7 wt. of formulation; where 7 by weight is based on 7 1.7 of the total dry solids weight of the formulation. In embodiments of Aime the formulations offered by the present sale include at least one filling effective in reducing the specific gravity of the formulation. in certain embodiments; The specific gravity of a formulation ranges from A to 0.7 to 1.75 Gen to 45,; and in certain embodiments; oo A reports certain incarnations; The specific gravity of a composition is less than about 0.9 less than about cA less than about 75 less than about 0.7 less than about 0.10 less than about 0.7 and in certain embodiments; 00 is less than about 0 in certain embodiments; The compositions offered by the present disclosure include an electrically conductive filling material. The composition can be given electrical conductivity and a shielding effectiveness of 1/85/ by incorporating conductive materials into metal particles or polymer coated particles (JB). Conductive elements may include; fibers; lattice elements; fibers; and mixtures thereof. The metal can be in the form of; for example, nickel, copper, fibrous filaments, particles, flakes, or pellets. Examples of metals include: Copper (JED Vo Tin 110; WL 15166. ¢ aluminum ¢ silver ¢ nickel can be used on polymer formulations and contain EMI/RFI particles] Other conductive materials to provide effective shielding graphite conductive polymers can also be used Conductive or fibers containing carbon or graphite polyaniline; polyanilines polypyrroles; polypyrroles polythiophenes such as polythiophene polyvinylene sulfide ' poly(p-phenylene) vinylene poly(m-phenylene) quinylene ¢ 0 And polyacetylene + polyphenylene phenylene lsu « polyphenylene sulfide polyacetylene and not exclusively calcium JE for example cage includes examples of non-electrochemical filling materials B. Fumed silica “polyamide aud poly” mica Kw; calcium carbonate microspheres “molecular sieve powder” fumed 511168 Yo

ONLY

microspheres titanium dioxide; chalks « alkaline blacks ; cellulose; zinc sulfide ¢ heavy spar 06; alkaline earth oxides » alkaline earth hydroxides » and the like. Filling materials also include high bandgap materials such as zinc sulfide and non-inorganic barium sae asl compounds. in certain embodiments; A conductive base composition may include an amount of non-conductive filler ranging from 1 7 by weight to 7 01 by weight based on the total weight of the base composition; and in certain embodiments from 3 # wt to 1 7 wt. in certain embodiments; The curing agent composition may include an amount of non-conductive filler ranging from less than 7 76 by weight and in certain embodiments from 0 70.5 to 74 by weight depending on the total weight of the curing agent composition. Fillers that impart electrical conductivity and EMI/RFI shielding effectiveness to polymer formulations are well known in the art. Examples of electrically conductive metal materials include: Noble metal-based filler 1016121-00 electrically conductive dad (ic) pure silver; noble metals plated with a noble metal such as silver—plated gold; non-noble metals non-noble metals 1 non-noble metals Jie cooper nickel or aluminum silver plated for example aluminum core particles or silver particles Platinum-coated copper; 91855 glass or 0185146 plastic or noble-metal-coated ceramics such as silver-coated glass microspheres; noble-metal-coated aluminum or noble-metal-coated plastic microspheres; noble-metal-coated mica; other noble-metal conductive filling materials YL Lad can use metal-based non-noble materials including, for example, non-noble metals coated with non-noble metal Jie iron particles clad with copper or nickel-coated copper; 005914 Cobalt; non-metallic materials coated with a non-noble metal; for example, nickel-plated graphite and non-metallic materials such as carbon black and graphite. Blends of conductive fill materials may also be used to meet desired conductivity; 5 Shielding effectiveness (EMI/RFI) Ruggedness; other characteristics appropriate for a specific application.

The conductive fill material used in formulations as per the present disclosure also cannot be of an adequate shape and size to give effective EMI/RFI shielding to the solidified composition. For example Jd) the fill material can take any form generally used in the manufacture of electrically conductive fill material; Including form (gp KU) flakes; sheets; particles; powder; irregular shape; fibres; and the like. In the sealing formulations of the present detection; a base composition may include nickel-plated graphite as a particle; powder; or a flake. In In certain embodiments the amount of nickel-plated graphite in a base composition can range from Ee 7 wt. to 88 7 wt., and in certain embodiments it can range from 5+0 7 wt. to Ve 7 wt., based on the total weight of the base composition. Certain embodiments Conductive filling material may include a nickel fibre. A base composition may include, for example (JB), an amount of nickel fibre, ranging from 7 7 wt to 7 01 wt and in certain embodiments from 7 4 wt to 7 8 wt, depending on the total weight of the base composition. Lead The use of carbon fibers, specifically carbon fibers treated with graphite, to impart electrical conductivity to the structures according to the present disclosure. Vapor phase pyrolysis and heat treatment graphite pyrolysis methods that are hollow or solid with a fiber diameter of 100 microns to several microns are electrically conductive. According to what is indicated in the American patent No. TAL YA; fine carbon fiber can be used; Nano-sized tubes or carbon fibers with an outer diameter of less than 1 μm to 10 nm as conductive fibres. An example of suitable graphitized carbon fiber for conductive fittings as per the present disclosure includes Panex® 30MF (Zoltek “Companies, Inc., St.

Louis, Mo.) has a diameter of 971 μm around a fiber with an electrical resistivity of 560,000 ohm-cm. The average particle size of an electrically conductive filler can be in a range useful for imparting YO electrical conductivity to a polymer-based composition. For example; In certain embodiments it can be seen

dew" particle size of one or more fillers ranges from YO, + µm to "You µm"fie in certain embodiments from YO, + µm to 75 µm and in certain embodiments from µm to 0 µm. /g (test method JO/84-5) and a porosity of 5000-4856 cm 7/001 g (absorption KTM (DBP -61 - 4). In certain embodiments, the filling material is electrically conductive carbon black (Cabot Corporation, Boston, Mass.) Black Pearls 2000. In certain embodiments; electrically conductive polymers may be used to impart or modify the electrical conductivity of Ye to existing detection compositions. Polymers with sulfur atoms contained in or adjacent to aromatic groups Double bonds, for example (JB) in polyphenylene sulfide and polythiophene, are well known to be electrically conductive. Other conductive polymers include, for example, compounds polypyrroles « polyaniline » poly(p-phenylene) vinylene « Jas Vo acetylene ©780©817/160a00. in certain embodiments; The polymers containing sulfur as a base composition can be polysulfide and/or polythioether compounds. As such, sulfur-containing polymers can include aromatic sulfur groups and sulfur atoms next to the conjugate double bonds, for example phenylcyclohexene-dimercaptodiactane (LS) groups to improve the electrical conductivity of 0-current detection compositions. . Compositions of the present disclosure can include more than one electrically conductive filling material and more than one electrically conductive filling material can be of similar or different materials and/or shapes. For example a wile sealant composition may include electrically conductive nickel fibers and electrically conductive nickel-coated graphite in powder form; particles or chips. YO can choose the amount and pattern of electrically conductive fill material to produce a sealing composition where; When you cross it, you show it

—yvo- and in certain embodiments; Yaufasd 150 laminar resistance (four-point resistance) of less than ohms/cm? . The amount and type of fill material can also be selected to provide shielding of 1.15 GHz Jif laminar impedance for an opening sealed with YA to 1 MHz effective over a frequency range of EMI/RFI sealing combination According to the current detection.

0 SEY Galvanic corrosion of dissimilar metallic surfaces and conductive compositions of the present detection can be reduced or prevented by adding OSE inhibitors to the formulation; and/or by appropriately selecting conductive fill materials. Corrosion inhibitors include strontium chromate strontium 0068 – calcium chromate; magnesium chromate,

chromate and mixtures thereof. US Patent No. 2,785,884 and US Patent No

Vo 5,775,714 on the use of aromatic triazoles to inhibit corrosion of surfaces

Aluminum and steel. in certain embodiments; A sacrificial oxygen scavenging agent may be used

0 with Jie sacrifice electrodes zinc in the form of a corrosion inhibitor. in certain embodiments; can include

Corrosion inhibitor to less than 701 by weight of the total weight of the electrically conductive composition. in embodiments

specific The corrosion inhibitor may comprise an amount from 77 by weight to 78 by weight of the total weight of the electrically conductive composition. Corrosion between dissimilar or metallic surfaces can also be reduced

Prevent it by selecting the type, quantity and characteristics of the conductive filling materials that include the composition.

in certain embodiments; A thiol-terminated polythiofull can comprise of about 7 560

by weight to about 7 90 wt of formula; from about 7 610 wt. to about 7 90 wt.;

from about 7 Ve wt to about 7 90 wt; and in certain embodiments; From about 88 wt 0 to about 0 7 wt of ASE where the percentage of 7 wt depends on the total wt

Dry solids of the formulation.

The uses

Combinations provided by the current list can be used; For example; in sealants;

coatings; Packaging Materials; and vessel assemblies. The sealant includes a formulation capable of producing a film

1+ has the ability to withstand operational conditions; eg moisture and hal degree and at least partially hinder the transmission of algal) eg water; fuel; and other liquids and gases. A coating composition includes a coating that is applied to the surface of a substrate, for example; to improve the properties of the substrate” eg appearance; adhesion wettability; corrosion resistance; Corrosion Ll fuel resistance and/or abrasion resistance +162. includes a sale receptacle structure useful in an electronic assembly to provide shock and vibration resistance and to exclude moisture and corrosive agents in certain embodiments; The sealant combinations offered by the current disclosure are useful; For example; As aerospace seals and liners for fuel tanks. in certain applications; A sealant composition is used to provide a seal between two panels such as; Take two (Ji) aluminum panels for example; in such applications the hardened thickness of the seal can be about 508 mm and exhibit an elongation greater than 2700 and a tensile strength greater than 1.77 MPa; It exhibits excellent fuel resistance and has a thermal stability of about VI to about VAY C. 3 Certain embodiments The thickness of the hardened seal can be from about 1117 mm to about 01011 mm; from about 754 mm to approx. VAY mm; from approx. TAY mm to approx. 195 “fede and in certain embodiments; approx. £TVA mm to approx. 554.7 mm in certain embodiments; the non-activated sealant formulation is stable for yi hours at least 0 _at least ? days; days; at least 8 days; | at least a day; and in certain embodiments at least 1 hour after formulation. It is desirable that at the desired time of use; the system is quickly activated and at a moderate temperature and/or power eg when the system is thermally activated the heat can be shed JAY from 5 seconds Jal from 101 seconds less than 001 second; and in certain embodiments; Less than 0 0 seconds. in

The dime Clad Gal Sle ge epoxy is ultrasonically fired using; For example (JB) a pressure of 1080 MPa at 10 kHz for Yoo ms. Alternatively, impact, shear, and/or crushing force can be applied to the sealing layer between two panels to induce hardening. © Fixtures, including sealing fluids, to be submitted in accordance with the current disclosure may be shed to any of the following:

variety of substrates. Examples of substrates to which a composite can be hammered could include Jie metals titanium + stainless steel ; and aluminium, which can be processed by the Aas method; primer coating; organically or chromate-coated; epoxy; urethane graphite sales

VE Composite of ¢Kevlar® fiberglass acrylics; And polycarbonate 001/5. in certain embodiments; The compositions offered by the present disclosure may be applied to a coating on a substrate; For example polyurethane coatings. The compositions offered in the present disclosure may be applied directly to a substrate surface or to a substrate by means of a suitable coating process known to those of ordinary skill in the art.

VO furthermore; Methods for preventing orifice leaks using a combination are given in accordance with the present disclosure. Methods include; For example; Lay the combination offered according to the current detection on the surface to prevent orifice leakage; and hardening composition. in certain embodiments; A method of sealing an orifice includes (a) applying a sealing composition offered in accordance with the present disclosure to one or more of the surfaces defining dai (b) assembling the surfaces defining the orifice; (c) Inducing energy to release the polycarbonate

0 epoxy from the packing material”; (d) sealant hardening; To provide a tightly closed opening. The sealant curing step involves allowing the sealant to solidify at ambient temperature without critically speeding up the curing process. in certain embodiments; Methods include (a) applying a sealant composition presented according to disclosure all to one or more surfaces defining an orifice; and (b) applying energy to release the polyepoxy from the encapsulating material.

M

in certain embodiments; A formulation can harden under ambient conditions after activation where ambient conditions refer to temperature from 10°C to YO°C and atmospheric humidity. in certain embodiments; A composition may be hardened under conditions including a temperature of 0°C to 001°Bde and a relative humidity of 0°C to .77000 in certain embodiments; 0 combination can harden at a higher temperature; eg JRA at least 30°C; 500 degrees at least; and in certain embodiments; 00 degrees Celsius at least. in certain embodiments; Formula can be hardened at room temperature; For example; YO degrees Celsius. in certain embodiments; A composition can be hardened when exposed to actinic radiation; For example, ultraviolet radiation as cash methods can be used

0 Sealing hatches on aerospace vehicles, including aircraft and aerospace vehicles. in certain embodiments; Formula can set without sticking in as little as about 6 hours; in less than about 11 hours; less than about YA hours; Jil about YE an hour ago; dy specific embodiments;

less than about $A an hour; After the polyepoxy (pOlyEpPOXY) has been released from the encapsulating material. The sclerotic structures detected by clin for example; rigid sealants; Vo exhibits acceptable characteristics for use in aerospace applications. in general; It is desirable that infusion mileages used in aviation and aerospace should exhibit the following characteristics: a peel strength greater than 7.5 on Aerospace Material Characteristics (AMS) 32658 substrates specified under dry conditions; after immersion in JRF for 1 ll and after immersion in a solution of 77 sodium chloride according to specification 'AMS 32658 lial 0' tensile strength between 7.0 MPa and 7.7 MPa; greater tear resistance than AVY; elongation between 77568 and 7700; and a hardness greater than 50 on the Durometer hardness scale A. These and other hardening sealant properties for aerospace and aerospace applications are disclosed gall at AMS 8 and are fully included here for reference. call is also desirable when hardening current detection assemblies used in aeronautical and aerospace applications; It shows an Asie YO ratio with volume inflation not exceeding 775 after immersion sad week at 00 degrees Lge and ambient pressure in

ONLY

4+ JRF Type A. Characteristics can be; cad) ad and/or other boundary values are appropriate for other sealing applications. so in certain embodiments; The combinations offered by the current disclosure are fuel resistant. According to use ola the term 'resistance to fuel' indicates that a composition which, when applied to a substrate and hardened, can provide © a hardened product eg sealant; exhibits a percentage increase in volume of not more than 6 in some cases not more than AYO In some cases not more than 7710 and in some other cases not more than 200 after immersion for one week at Te temperature and ambient pressure in the reference fluid (JRF) Jet Reference Fluid of type | according to similar methods. Described in ASTM 0792 (American Society for Testing and Materials) AR 3269 AMS 0 (Specification for Aerospace Materials).(JRF) Jet Reference Fluid Type |" according to its use for determining fuel resistance; has the following composition : toluene 10|0606: 71 + YA by volume; cyclohexane (technical): 71 + YE by volume; isooctane ZY + YA: isooctane by volume; dibutyl gla trisulfide 1 : tertiary dibutyl disulfide + 0# ,70 by volume (see AMS 2629, issued July 1, 1989, 5 3.1.1 etc., available from SAE((Society of Automotive Engineers) 0 in certain embodiments; formulations available which was done Presented here as an example of a rigid product; sealant It exhibits a tensile elongation of at least 72000 and a tensile strength of at least YY MPa when measured according to the procedure described in 3279, 1 5 3.3.17.1 (AMS test procedure AS5127/1, § 1.7 Yo in certain embodiments ; formulations provide a hardened product eg; seal” showing 58 overlap shear greater than 1.7 MPa; eg at least 1.5 MPa; VY is MPa on JY) and in some cases ; VV MPa minimum when measured according to the procedure described in SAE ASS5127/1 Paragraph A=Y

=« _ in certain embodiments; Leaking fluid including composition is introduced according to the current detection meets or exceeds the detected openings are also provided; Ly including slots for aerospace vehicles; Sealed with the fittings offered by the current disclosure.

in certain embodiments; Electrically conductive sealant composition 2 provided according to the present disclosure exhibits the following properties measured at room temperature following exposure to 710°C for VE hours: a surface resistivity of less than 1 ohm/sq; tensile strength greater than 0.7 MPa; greater than ARE elongation and 0 adhesion failure measured in accordance with MIL-C-27725 in certain embodiments; A hardening sealant offered according to the current configuration exhibits the following characteristics

a when hardened for 2 days at 1 (dd al) 1 day at 01 degrees YEP 6 and 1 day at 997 degrees YEP : dry hardness of 5 tensile strength of Y, Y MPa; elongation of 7 and after 7 days in JRF; Faia hardness; tensile strength of 7.15 MPa; and an elongation of 47 77. In certain embodiments; The compositions presented by the present list show a hardness of (V) Shore A days

11 stiffness) greater than 10; greater than 10; greater than 10; and in embodiments (Alma greater than tv) tensile strength greater than 1.05 MPa; greater than 1.6 MPa greater than 0.7 MPa in Aza embodiments greater than 0.4 MPa elongation greater than ARE greater than YAR greater than VATE and in Alma embodiments greater than 110 and the volume increase after exposure to JRF (V days) less than WA 0

0 Examples Embodiments given in accordance with the present disclosure are also illustrated by reference to the following examples; Jie, which describes formulations including thiol-terminated polythioethers and epoxy encapsulated compounds and uses of those formulations. It will become clear to those skilled in the field that many modifications can be made to both materials and methods.” Practically without straying from the detection range.

Lakr

— ¢ \ —

1 example

Micro-encapsulated epoxy sealant composition

A mixing step was performed in a plastic container with a lid. ad Permapol® P3.1E has been added

15.58 (©) g; poly of thiol-terminated ethers available from PRC-Desoto International, Inc.

¢(Inc, Sylmar, CA) Calcium Carbonate «(a> A, +) calcium carbonate triethylene di

amine (+,YY) triethylene diamine (5 g) Lipocapsule™ LT-81381 (1¢, ¥ g);

epoxy resin coated; Available from Technologies 100a) to container. The container is placed in

Rapid mixer (FVZ 600 DAC) and blended for Ve sec at YY ee rpm. A portion of the mixture is left in the plastic container at room temperature. after ; weeks;

The mixture remained liquid and was clearly not solidified. A second part of the mixture was crushed in

Porcelain mortar for 90 minutes. The material formed a hard elastic plastic after weeks with a hardness value of

Vo Bohdat / ©5001. A third gia of the blended material was placed on the teeth of a screw. The screw has been turned

in a matching nut. and by means of mechanical shearing associated with the coil winding; The material formed a soft elastomer Ve in VE hours.

Then, the jee-elastic solid was soaked in a Jet Reference Fluid type for 1 days at 110 °C. The increase in volume was 4 77 and the volume loss was 77,4 measured according

SAE AS 5127 L.L

Finally, it should be noted that there are alternative ways to implement the renders shown here. Accordingly, 0 -_ present incarnations should be viewed as illustrative rather than exhaustive. Furthermore; Must not

The claims are construed as limiting the particulars set forth herein and extend to their full extent and equivalents.

Claims (1)

These are the elements of protection - 1 A curable aerospace sealant composition comprising: 0 6 wt. to 96660 wt. of thiol-terminated polythioether; where polythioether ju) of thiol-terminated includes polythioether ji of the thiol-terminated of formula slid (1); © -0112(2-5-41-0 )-142-0(0)-0112(0-0)-5-[-1[+a-(1); each 41 independently includes 62-10 cycloalkanediyl 66-8 “alkanediyl” 06-14 heterocycloalkanediyl 65-8 » alkanecycloalkanediyl « or -a(-43a011-)-0[-5-2(-43a011-)]-” where: Ve 5 is an integer from AY 1; 0 is an integer from zero to 5; is an integer of ? to 10; each R3 independently contains a hydrogen or a methyl ; and every 6 is selected independently from -0- ; -5-; and-46l1-, where RO is selected from Vo hydrogen and methyl; Each 42 independently includes 61-10 cycloalkanediyl 66-8 « alkanediyl « 06-14 alkanecycloalkanediyl » or —[(-CHR3-)s-X-]q—(—CHR3-)r- where “r qs 3 is as defined by RT (AM) an integer from zero to +; an Ye is an integer from 1 to 10; and m is an integer from AY 1 (b) 0,5 wt. to 96700 wt. Micro-casings comprising a polymeric shell shell 0017006116 and a suspended polyepoxy solvent « The polymeric shell comprises gelatin and polyoxymethylene urea; polyoxymethylene urea and polyepoxy includes / bisphenol / epichlorohydrin derived from epoxy resin; f © (c) amino catalyst; Where the amino catalyst comprises triethylene diamine 1,8-diazabicycloundec—(DBU) 7-806; YY] octane-1,4 SW (DABCO) diazabicyclo[2,2.2]octane amine isophorone C6-10 5 “(IPDA) diamine primary amine or a combination of the above; Ve, where the weight % depends on the total weight of the solids in the curable formula. “- Composition Ga, of claim 0 wherein a thiol-terminated polythioether comprises (a) a thiol-terminated polythioether of formula (Y) or __polythio A thiol-terminated polythioether of formula (IY) or a combination thereof: (Y) HS-R1-[-S—(CH2)p-O—-(R2-O)m—-(CH2) 2-S-R1-]n-SH (iv) {HS-R1-[-S—(CH2)p—O—(R2-O)m—(CH2)2-S-R1-]n-S- V'-}zB each 41 independently includes 62-10 C6-14 “cycloalkanediyl 66-8 alkanediyl heterocycloalkanediyl 65-8 alkanecycloalkanediyl 0” or “—[(—CHR3-)s—X- ]q—(-CHR3-)r- where: is an integer from TAY 9 is an integer from 1 to 0 is an integer from ? to 10; R3 JS Yo independently contains hydrogen hydrogen or methyl; and — ¢ ¢ — each X independently contains -0- 2 -and-e; or R Cua ¢ -NR - selected from hydrogen or methyl; Each R2 independently includes 61-10 C6-14 « cycloalkanediyl 06-8 » alkanecycloalkanediyl “ or —[(-CHR3-)s-X-]q—(—CHR3-)r- where “r” qs Xs “R3© is as defined by ¢R1 m is an integer from zero to $0 0 is an integer from 1 to FRAX m is an integer from AY 1 8 denotes inverse valence 2; A polyfunctional operator with a vinyl terminal ending in B(-V)z 0 where: > is an integer of ? to 1; and each 1/ is a group consisting of a terminal vinyl group; and each -V'= is derived from the reaction of -1/ with a 1 thiol “©-composition according to the protection element” where the pOlyepoxy is released from the microfilaments by applying an energy selected from heat; mechanical force Ultrasonics ¢ or a combination of any of the above. ;- Composition according to Clause 0 wherein the poly epoxy 001788007 encapsulated from 0 microcasings is fired at a temperature from Av to 011 °C Jase 0 Composition according to Claim 0 where it includes Polyepoxy on polyepoxy has a molecular weight from Yeo Dalton to Osh 5001 Yo 1 The composition according to claim 1 includes a prepolymer containing sulfur with a thiol end additional. c ¢ — “- the combination in accordance with claim 7; wherein the prepolymer containing an additional thiol-terminated 0aa50 sulfur includes polythioether jf with a thiol-terminated ; polysulfide ade dg thiol-terminated; polyformal thiol-terminated; or a combination of any of the above. lo}—A composition according to claim 1 wherein the composition has a service life of YE hours to ; weeks. 4- Composition of claim 1; formulated as sealant 7"-0 A method of sealing a surface involving: (a) applying the composition of claim 4 to a surface; and (b) applying energy For the release of polyepoxy from microcasings to seal the surface.-11 Yo Method Gg of Claim 01 where the energy transfer includes the transfer of thermal energy -1 Surface sealed with the composition By For protection A YY 0 Method according to protection Gus 00 Energy transfer includes mechanical energy transfer .mechanical energy 4- curable composition pursuant to claim 1 wherein the sole includes 9001 wt. to 0 7065 wt. of filler. Yo ONLY 1- The curable composition according to claim 0, where the amino catalyst includes triethylene diamine. 7- ALE curable aerospace sealant © includes: 0 6 wt. to 9660 wt. of polythioether ju) of thiol-terminated; where the thiol-terminated poly(ji) of polythioether includes a thiol-terminated polythioether ji of the formula slid (1); -41-1[0a-0112(2- 5)-0112(0-0-142-0(0)-5-[-1]+a-(1); 0 a where: each 41 independently includes 62-10 cycloalkanediyl 66-8 « alkanediyl » 06-14 heterocycloalkanediyl 65-8 » alkanecycloalkanediyl » or -0(-43a0-)-10[-5-2 (-43 A011-)]-; where : is an integer number of TAY 05 0 is an integer from zero to 5; is an integer of ? to 10; each R3 independently contains a hydrogen or a methyl ; and each X is independently selected from -0- « —S— and -6>a- where RO is selected from hydrogen and methyl ; 66-14 « cycloalkanediyl 66-8 » alkanediyl 61-10 independently includes R2 every 0 “r” qs where —[(-CHR3-)s-X-]q—(—CHR3-)r- or « alkanecycloalkanediyl (RT) which is as defined by 3 to + 1; is an integer from 1 to 10; and 1 is an integer from 1 AY Integer of ap YO ONLY and (b) 0.5 wt to 96,700 wt micro-enclosures comprising a polymeric shell and a polyepoxy suspended in a solvent; where; The polymeric shell includes gelatin and polyoxymethylene urea; and © polyepoxy includes / bisphenol / epichlorohydrin derived from epoxy resin ; and (c) jas amine catalyst, where the weight % depends on the total weight of the solids in the curable formula. ONLY The validity period of this patent is twenty years from the date of filing the application, provided that the annual financial fee is paid for the patent and that it is not invalid or forfeited for violating any of the provisions of the patent system, layout designs of integrated circuits, plant varieties, and industrial designs, or its executive regulations issued by King Abdulaziz City for Science and Technology; Saudi Patent Office P.O. Box TAT Riyadh 57??11 ¢ Kingdom of Saudi Arabia Email: Patents @kacst.edu.sa